Microelectrodes for electrochemical gas detectors

ABSTRACT

An electrochemical gas sensor having an electrode with a catalyst distributed on a porous surface is described. The porous surface can be a polytetrafluoroethylene tape. Alternate embodiments include layered or stacked electrodes.

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority of U.S. Provisional Application Ser.No. 61/830,392 filed Jun. 3, 2013, whose disclosures are incorporatedherein by reference.

FIELD

This application pertains to electrochemical gas detectors, whichincorporate microelectrodes. More particularly, this applicationpertains to electrochemical gas detectors, which include an electrodecomprised of a catalyst deposited onto a porous surface.

BACKGROUND

Electrochemical gas sensors using microelectrodes have a number ofbenefits, such as the ability to use fast scanning voltammetricmeasurements, utilizing features such as convergent diffusion andpotentially being simpler to construct than conventional gas diffusionelectrodes. However they also suffer from disadvantages. In particularit is more difficult to achieve a reliable 3-phase region, i.e., aregion where gas does not have to diffuse a long distance through theelectrolyte before reaching the sensing electrode(s).

The analyte gas can dissolve in the electrolyte and give rise to abackground current which remains after the target gas is removed,resulting is slow response times and background current errors.

This issue is normally overcome in conventional gas sensors by ensuringthat all of the target gas is consumed by the sensing electrode (e.g.,via capillary limitation of flux to a gas diffusion electrode). Howeverthe design of gas diffusion electrodes is complex, especially when usingnon-aqueous electrolytes such as ionic liquids, and the resulting largesurface area and hence double layer capacitance means that dynamicelectrochemical techniques such as scanning voltammetry are notfeasible.

An example of the current state of the art in microband electrodes arethose manufactured by Nanoflex®(http://www.nanoflex.com/Products/Product/Platinum_Substrate) whichcomprise band electrodes within wells of micrometer dimensions.Previously people have also used line electrode devices deposited onionic conducting substrates (Kirsi Wallgren, PhD thesis 2005, Universityof Nottingham and references therein). Microband electrodes can be madevia sandwich structures using, for example, micromachined silicon layersor line electrodes on the surface of a substrate. These approaches donot address the issue of ensuring easy gas access to the sensingelectrode, since it is immersed within the electrolyte (which may beeither a solid or liquid).

In accordance herewith, methods and structures are provided forutilizing microelectrodes and particularly microband electrodes in sucha way as to ensure rapid gas access to the sensing electrode(s) and/orto compensate or correct the sensor behavior for variations in thedegree to which the sensing electrode is wetted. The attached figuresillustrate various aspects of embodiments hereof.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A illustrates an approach for locating the shape and location ofthe electrolyte meniscus by EIS.

FIG. 1B illustrates a well with layered microband electrodes andcounter/reference electrode(s).

FIG. 1C illustrates an oxygen pump sensor concept.

FIG. 1D illustrates a sensing electrode located at the interface betweenthe diffusion barrier and electrolyte.

FIG. 2A illustrates a configuration where a solid electrolyte andelectrodes such as gas diffusion electrodes are used ‘end on’ to createa microband type of system.

FIG. 2B illustrates a configuration where electrodes and electrolyteprotrude from the sensor.

FIG. 2C illustrates a configuration where a solid electrolyte, a filter,and electrodes such as gas diffusion electrodes are used ‘end on’ tocreate a microband type of system.

FIG. 2D illustrates a stacked configuration where several solidelectrolytes and electrodes, such as gas diffusion electrodes, are used‘end on’ to create a microband type of system.

FIG. 3A illustrates a simulated detector's structure.

FIG. 3B illustrates expected results of the detector of FIG. 3A.

DETAILED DESCRIPTION

The use of non-gas diffusion electrodes in electrochemical gas sensorscan alleviate some problematic issues that persist in traditionalsystems, such as humidity transients, low sensitivity, and slow responsetimes. The novel electrochemical gas sensor described herein includes asensing electrode fabricated by depositing a catalyst onto a poroussupport material. The catalyst can be platinum or another noble metal orother catalysts or mixtures thereof known in the art. The porousmaterial can be polytetrafluoroethylene (PTFE) or other porous materialsknown in the art. This catalyst can be deposited randomly or uniformly.On deposition technique is vacuum sputtering, which when utilized,yields a thin, fully wetted electrode having pores through which a gascan travel. The electrode gives negligible humidity transients when usedwith an electrolyte such as sulfuric acid, phosphoric acid,ethylmethylimidazolium hydrogen sulfate (EMIM HS) or other knownelectrolytes or mixtures thereof. The electrode also gives fast responsetimes to hydrogen sulfide gas when used with the above electrolytes.

The electrolyte can be present as a free liquid, absorbed in a wick orseparator material, or absorbed in a solid support. The solid supportthat the electrolyte is absorbed on can be polybenzimidazole film.

FIGS. 1A-1D illustrate aspects of one method of improving on a single,line or band or other type of electrode. One or more sensing electrodesare coated with a meniscus of electrolyte. The upper most electroderapidly responds to changes in the gas phase due to the thinly wettedelectrolyte layer. ‘Auxiliary’ electrodes deeper into the electrolytewill not respond so quickly and can be used to measure dissolved gas inthe bulk of, or spatially varying within, the electrolyte and can thenbe used to correct the main sensing electrode signal for the effect ofthese background currents.

This approach requires the shape and location of the electrolytemeniscus to be well defined, which in practice does not always occur—forexample changes in temperature and or hydration level of the electrolytecan cause the electrolyte layer to move. By performing measurements suchas electrochemical impedance spectroscopy (EIS) on the differentelectrodes within the structure in FIG. 1A, the position of theelectrolyte layer can be determined, and the resulting calculatedgeometry used in combination with current measurements to compensate forbackground currents. In extreme cases, the meniscus may even move to theextent that the uppermost electrode is no longer in contact with it, inwhich case the next electrode down will be used as the sensingelectrode.

FIG. 1B illustrates one practical implementation of this approachcomprising a well with layered microband electrodes andcounter/reference electrode(s). FIG. 1C shows an oxygen pump sensorconcept based on a similar approach. An optional solid PTFE oxygendiffusion barrier can be used as a diffusion limiter and/or retainer forliquid electrolyte. The sensing electrode may beneficially be located atthe interface between the diffusion barrier and electrolyte as shown inFIG. 1D. The counter electrode may be a conventional gas diffusionelectrode or similar for oxygen generation, a further electrode orelectrodes may be included to measure and compensate for backgroundcurrents.

FIG. 2A illustrates a configuration where a solid electrolyte andelectrodes such as gas diffusion electrodes are used ‘end on’ to createa microband type of system. In this case the stack could be implementedwith a commercial membrane electrode assembly (MEA) or similarstructure. FIG. 2B illustrates that the electrodes and electrolyte couldprotrude from the sensor and not be flush as in FIG. 2A. Variations onthis approach include filters, FIG. 2C, and stacked systems to increaseelectrode areas as in FIG. 2D.

Structures as described above and illustrated by the attached can befabricated using, for example, screen printing, MEMS fabrication,multilayer printed circuit boards (e.g., with platinum plated copper),or techniques such as those used for making film and foil capacitors ormultilayer batteries.

FIG. 3A illustrates a simulated detector's structure in accordanceherewith. FIG. 3B illustrates expected simulated results of the detectorof FIG. 3A, namely, the results of a finite element model where thesignal from an auxiliary electrode is used to compensate the mainelectrode signal for the slow secondary response due to dissolved gas.

From the foregoing, it will be observed that numerous variations andmodifications may be effected without departing from the spirit andscope of the invention. It is to be understood that no limitation withrespect to the specific apparatus illustrated herein is intended orshould be inferred. It is, of course, intended to cover by the appendedclaims all such modifications as fall within the scope of the claims.

Further, logic flows depicted in the figures do not require theparticular order shown, or sequential order, to achieve desirableresults. Other steps may be provided, or steps may be eliminated, fromthe described flows, and other components may be add to, or removed fromthe described embodiments.

1. An electrochemical gas detector comprising: a well with multiplelayered microband electrodes, which are used to compensate for dissolvedgases in the electrolyte, and at least one of a counter, or a referenceelectrode.
 2. An electrochemical gas detector which includes a stackcomprising a plurality of elements, each having a solid electrolyte andelectrodes such as gas diffusion electrodes, where the gas access is toexposed ends of the electrode stack.
 3. An electrochemical gas sensorcomprising an electrode including a catalyst deposited on a porousmaterial wherein the catalyst is deposited by vacuum sputtering thecatalyst onto the porous material.
 4. (canceled)
 5. The electrochemicalgas sensor of claim 3 wherein the catalyst comprises platinum or anothernoble metal.
 6. The electrochemical gas sensor of claim 3 wherein theporous material comprises polytetrafluoroethylene.
 7. Theelectrochemical gas sensor of claim 3 further comprising an electrolyte.8. The electrochemical gas sensor of claim 7 wherein the electrolytecomprises sulfuric acid, phosphoric acid, or ethylmethylimidazoliumhydrogen sulfate.
 9. The electrochemical gas sensor of claim 7 whereinthe electrolyte comprises one of a free liquid, is absorbed in a wick orseparator material, of is absorbed in a solid support.
 10. Theelectrochemical gas sensor of claim 9 wherein the electrolyte isabsorbed in polybenzimidazole film.
 11. The electrochemical gas sensorof claim 9 wherein the electrolyte is absorbed in a wick.
 12. Theelectrochemical gas sensor of claim 9 wherein the electrolyte comprisesa free liquid.
 13. The electrochemical gas sensor of claim 7 wherein theelectrolyte comprises sulfuric acid.
 14. The electrochemical gas sensorof claim 7 wherein the electrolyte comprises phosphoric acid.
 15. Theelectrochemical gas sensor of claim 7 wherein the electrolyte comprisesethylmethylimidazolium hydrogen sulfate.
 16. The electrochemical gassensor of claim 4 wherein the catalyst comprises platinum and the porousmaterial comprises polytetrafluoroethylene tape.
 17. The electrochemicalgas sensor of claim 8 wherein the catalyst comprises platinum, theporous material comprises polytetrafluoroethylene tape, and theelectrolyte comprises phosphoric acid.
 18. The electrochemical gassensor of claim 8 wherein the catalyst comprises platinum, the porousmaterial comprises polytetrafluoroethylene tape, and the electrolytecomprises sulfuric acid.
 19. The electrochemical gas sensor of claim 8wherein the catalyst comprises platinum, the porous material comprisespolytetrafluoroethylene tape, and the electrolyte comprisesethylmethylimidazolium hydrogen sulfate.
 20. The electrochemical gassensor of claim 9 wherein the catalyst comprises platinum, the porousmaterial comprises polytetrafluoroethylene tape, the electrolytecomprises ethylmethylimidazolium hydrogen sulfate, and the electrolyteis absorbed in a solid support.
 21. The electrochemical gas sensor ofclaim 7 where the electrolyte comprises one of an aqueous, ionic liquidor polymeric electrolyte.
 22. The electrochemical gas sensor of claim 1which includes at least one sensing electrode and wherein that electrodeis coated with a meniscus of electrolyte.
 23. The electrochemical gassensor of claim 22 which includes at least a second sensing electrodedisplaced toward the electrolyte from the at least one sensing electrodewherein the second sensing electrode responds to measured dissolved gasin the bulk of, or spatially varying within the electrolyte, to correctthe signal of the at least one sensing electrode for the effect ofbackground currents.
 24. The electrochemical gas sensor of claim 1 whichincludes an oxygen diffusion barrier or retainer for an electrolyte inthe well wherein a sensing electrode is located at an interface betweenthe diffusion barrier and the electrolyte.
 25. The electrochemical gassensor of claim 2 which includes at least first, second gas diffusionelectrodes with a solid electrolyte therebetween and with an end regionthat includes an end portion of each electrode and an end part of thesolid electrolyte all of which are gas accessible.
 26. Theelectrochemical gas sensor of claim 25 wherein the electrodes and thesolid electrolyte are carried by a support.
 27. The electrochemical gassensor of claim 26 where relative to an end of the body, the end regionis located at one of, flush with the end of the body, extending from theend of the body, or recessed relative to the end of the body.
 28. Theelectrochemical gas sensor of claim 27 which includes a plurality offirst, second electrode combinations with each separated by electrolytewherein members of the plurality are carried by a common housing.